EP2878023B1 - Elektrochemischer engergiespeicher mit einem zusatzstoff - Google Patents
Elektrochemischer engergiespeicher mit einem zusatzstoff Download PDFInfo
- Publication number
- EP2878023B1 EP2878023B1 EP13728379.2A EP13728379A EP2878023B1 EP 2878023 B1 EP2878023 B1 EP 2878023B1 EP 13728379 A EP13728379 A EP 13728379A EP 2878023 B1 EP2878023 B1 EP 2878023B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- additive
- compound
- electrolyte
- alkaline earth
- earth metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000654 additive Substances 0.000 title claims description 62
- 230000000996 additive effect Effects 0.000 title claims description 54
- 239000011521 glass Substances 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 57
- 239000000843 powder Substances 0.000 claims description 55
- 239000003792 electrolyte Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000004146 energy storage Methods 0.000 claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 238000012983 electrochemical energy storage Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims 3
- 229910004074 SiF6 Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 47
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 229910018068 Li 2 O Inorganic materials 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 5
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002352 surface water Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 238000005247 gettering Methods 0.000 description 3
- 239000002241 glass-ceramic Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraethylene glycol dimethyl ether Natural products COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- 229910003001 Li-Ni-Co-Mn-O Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- 229910008284 Si—F Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical class O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000032677 cell aging Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004761 hexafluorosilicates Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an electrochemical energy store with an additive.
- Energy storage or additives which contain in particular glass powder, are known for example from the following documents: DE 10 2009 056 756 A1 . WO 2011/124347 A1 . WO 2012/045514 A2 . WO 2012/045662 A2 . DE 10 2011 914876.4 . JP 2005-11614 A , Glass-containing fuel cells are in Lara et al., Solid State Ionics 170 (2004) 201-208 described. US 2006/0292446 A1 respectively. US Pat. No. 7,655,358 B2 describe a rechargeable lithium battery with a positive electrode containing as a positive-active material, a lithium-containing transition metal compound and an additive.
- the additive comprises at least elemental Si, B, Ge, Ga, Mg, Ca, Sr, Ba or at least one oxide of these elemental substances.
- the elements or oxides of these elements react with RF unwanted in the battery.
- SiO 2 reacts with HF to form H 2 SiF 6
- the alkaline earth metal oxides (RO) react with HF to form alkaline earth metal fluorides (RF 2 ).
- Future energy storage such as lithium-ion batteries for mobile or stationary applications, require an improvement of energy storage in terms of their safety, cost and weight, the latter with a view to increasing the specific energy or power density.
- the lifetime in particular of energy storage devices containing lithium ions both during operation (charging or discharging operations) and during the general service life (calendar life) also plays an important role.
- the life-degrading effects are, for example, the increasing formation of a surface layer on the anode (Solid Electrolyte Interphase (SEI)) with the consequence of increasing lithium deficiency and increasing the internal resistance.
- SEI Solid Electrolyte Interphase
- HF hydrogen fluoride
- the formation of HF depends in particular on the water content in the energy store, wherein the water reacts with fluorine-containing conductive salts. Moisture (water) can get into this during the manufacture of the energy storage in particular. But even during the operating time, due to the smallest leaks, e.g. In the area of the polymer-carrying contact feed-through, moisture creepingly enters the energy store.
- additives e.g. to the liquid electrolyte of an energy storage, e.g. a lithium ion cell, minimized (cryogenic additives, SEI formation enhancers or controllers, flame retardants, wetting agents, anion receptors, overcharge protection additives, water or acid scavengers, smooth lithium deposition additives, etc.).
- an energy storage e.g. a lithium ion cell
- minimized cryogenic additives, SEI formation enhancers or controllers, flame retardants, wetting agents, anion receptors, overcharge protection additives, water or acid scavengers, smooth lithium deposition additives, etc.
- Behind the additives are almost exclusively organic, aromatic or metal-organic compounds, which often contain halogens or sulfur. These are therefore often toxic, also expensive and often easily ent-flammable due to lack of temperature resistance.
- a processable solid-functional additive for the local protection of a HF and water-sensitive cathode material such as LiMn 2 O 4 (LMO) from HF and water.
- LMO LiMn 2 O 4
- NiO or ZnO is added. This can be optionally integrated by coating the electrode particles or the entire electrode or by admixture with the cathode material in the composite.
- an electrochemical energy store in particular a lithium-ion cell, with an anode, a cathode, a separator and with at least one additive
- the additive contains at least one silicon and alkaline earth metal-containing compound V1 which forms at least one compound V3 in contact with a fluorine-containing compound V2 in the energy store, the compound V3 being selected from the group of the silicon- and fluorine-containing, lithium-free compounds V3a, the alkaline earth metal and fluorine-containing, lithium-free compounds V3b, the silicon, erdalkalimetall- and fluorine-containing, lithium-free compounds V3c or combinations thereof
- the compound V1 is a glass powder, in particular a glass powder containing at least one as glass composition constituents Alkaline earth metal oxide and silica, the glass powder having the following glass composition ingredients (in% by weight): SiO 2 15 - 75 BaO 0 - 80 ZrO 2 0 - 15 Li 2 O
- At least one compound V3 forms in contact with a fluorine-containing compound V2 in the energy store.
- the compound V3 is in particular a non-volatile, non-gaseous compound which binds the fluorine very well (under normal conditions of use of the energy store).
- the compound V1 is preferably a glass powder having the following glass composition ingredients (in% by weight): SiO 2 15 - 45 BaO 10 - 80 ZrO 2 0 - 15 Li 2 O 0 - 25 P 2 O 5 0 - 20 Al 2 O 3 0-10 CaO 0 - 30 MgO 0 - 30 MgO + BaO + CaO ⁇ 30 NiO 0-10 PbO 0-10 ZnO 0-10 F 0 - 5.
- the compound V1 is preferably a glass powder having the following glass composition ingredients (in% by weight): SiO 2 20 - 40 BaO 40 - 80 ZurO 2 0 - 8 Li 2 O 0 - 15 P 2 O 5 0 - 15 Al 2 O 3 0-10 CaO 0 - 30 MgO 0 - 30 MgO + BaO + CaO ⁇ 30 NiO 0-10 PbO 0-10 ZnO 0-10 F 0 - 5
- the compound V3a or the compound V3c preferably contains [SiF 6 ] 2- groups.
- the compound V3b or the compound V3c preferably contains MSiF 6 , wherein M is at least one alkaline earth metal element, in particular barium.
- the compound V3b or the compound V3c preferably contains MF 2 , where M is at least one alkaline earth metal element, in particular barium.
- the compound V3 is preferably formed on the surface of the compound V1.
- the additive is preferably part of an electrode, an electrolyte or a separator of an energy store.
- the additive preferably contains at least one silicon and alkaline earth metal-containing compound V1, which forms at least the compound V3 in contact with HF in the energy store.
- the better binding of HF, the better binding of H 2 O or the lower release of H 2 O is preferably qualitatively evident by cyclic voltammetry.
- the HF property or preferably additional H 2 O properties of a glass powder are compared with the corresponding properties of an Al 2 O 3 powder, both powders having a comparable average grain size and the three properties are determined under comparable conditions.
- the better binding of HF and the better binding of H 2 O are probably based on a better chemical bonding of these substances by the appropriate glass powder than by the comparable Al 2 O 3 powder.
- the lower release of H 2 O is presumably based on a better adsorption of H 2 O in the liquid electrolyte by the glass powder than by the comparable Al 2 O 3 powder.
- At least one of the three properties of the additive preferably improves with time, in particular within a period of up to 2 to 5 days after contact of the additive, in particular of the glass powder, with the electrolyte. That, for example, the better binding of HF gradually improves over time from the completion of the energy storage, so it is initially bound little HF and then more over time.
- the electrolyte is preferably a nonaqueous electrolyte, an electrolyte based on carbonic solvents and / or the electrolyte preferably contains at least LiPF 6 as a conducting salt.
- the energy store is preferably a lithium-ion cell.
- the energy store preferably contains an anode, a cathode and a separator. Surprisingly, it has been shown that much better electrochemical energy stores are obtained by these simple measures.
- electrochemical energy storage in the context of the invention includes primary and secondary batteries, accumulators, lithium-ion cells, lithium metal cells and capacitors. Rechargeable lithium ion cells are preferred.
- glass powder in the sense of the invention comprises glass powder and / or glass ceramic powder.
- fluorine-containing compound V2 includes HF.
- HF in the sense of the invention includes HF, fluorine and fluoride ions.
- lithium-free compound in the sense of the invention means that the compound is free of lithium except for unavoidable traces, preferably the lithium-free compound contains no lithium. Ultimately, it's about as impossible to demobilize any lithium of the energy storage in the compound V3.
- the glass powder in contact with the electrolyte forms a sparingly soluble Si-F compound in the electrolyte and thus bonds HF more effectively.
- the formation of the sparingly soluble fluoride is not necessarily but preferably carried out on the surface of the glass powder particles.
- the formation of finest colloids of the poorly soluble fluoride phase in the electrolyte is conceivable.
- the electrochemical energy store is preferably a rechargeable lithium-ion cell.
- the glass powder is part of a separator of the energy store, in particular a filler and / or a coating of a separator and / or part of an electrode of the energy store, in particular and / or anode, and preferably the glass powder is integrated or integrated in the electrode applied their surface.
- the glass powder is contained in the electrolyte of the energy store, in particular in a solid electrolyte and / or a liquid electrolyte.
- the preferred solution according to the invention also describes the use of a functional, glassy or glass-conducting or ceramic powdery additive of a lithium ion cell.
- the ingredient chemically binds harmful fluoride.
- water is chemically bound and it will continues to prevent the development of HF. The bonding of HF and water takes place under service life as well as under potential load. The delivery of surface water of the additive is additionally minimal.
- the electrochemical energy store contains a glass powder having the following composition range (in% by weight).
- the molar ratio of alkaline earth metal oxide to silica is in the range of ⁇ 0.65-1.0.
- Composition area 1 is a composition of Composition area 1:
- the electrochemical energy store particularly preferably contains a glass powder which has the following composition ranges (in% by weight):
- Composition area 2 is a composition of Composition area 2:
- Composition area 3 is a composition of Composition area 3:
- Composition area 4 is a composition of Composition area 4:
- Composition area 5
- refining agents in conventional amounts of up to 2 wt .-% can be added in all composition ranges.
- refining agents SnO 2 As 2 O 3 , Sb 2 O 3 , sulfur, CeO 2, etc. can be used.
- polyvalent refining agents are unavoidable, their content should be kept as low as possible, ideally below 500 ppm, for reasons of electrochemical stability.
- refining agents may possibly be completely dispensed with, provided that the glass is close to the application, ie produced as a fine powder, and the requirement for freedom from bubbles is not high.
- the following items should, even if they can not be leached into the electrolyte, in the smallest possible quantities ⁇ 1000 ppm, preferably ⁇ 500 ppm, particularly preferably ⁇ 150 ppm may be contained in the glass powder: Fe, Ni, Cu, Bi.
- SiF 6 compounds mentioned above which are formed according to the invention, are sparingly soluble alkaline earth hexafluorosilicates. Any formation of corresponding lithium salts, such as in JP 2005-011614 A described, is undesirable in the sense of the application, since the system is deprived of lithium, which accordingly can not be used for energy storage. In the JP 2005-011614 A Lithium is deliberately demobilized in case of abnormal cell behavior.
- the present invention thus provides an energy store with a non-toxic, temperature-stable inorganic additive (solid-state additive) for flexible use in all areas of an energy store, e.g. a rechargeable lithium-ion cell, ready to make their use more durable.
- an energy store e.g. a rechargeable lithium-ion cell
- the invention provides functionality for binding harmful HF and water in an energy store, which are the influencing factors of cell aging. The binding takes place in the energy store when applied potential as well as during life.
- the added glass powder gives off much less surface water compared to the other materials used in the energy storage.
- the glass powder as an additive is shown in the embodiments AB 1 to AB 28.
- the glass powder was placed in a battery electrolyte and allowed to stand at 60 ° C for seven days. After separating the electrolyte and drying the material, the BaSiF 6 (eg on the surface of the glass powder) can be detected by XRD (X-ray powder diffractometry), alternatively EDX and SEM in the case of the formation of non-crystalline phase.
- the electrolyte used is essentially a mixture of one or more nonaqueous, preferably carbonate solvents and at least one fluoride conducting salt.
- LiPF 6 was used as the conductive salt.
- the solvents can be used alone or as suitable mixtures.
- Exemplary blends are EC / DMC in the ratio 50/50 (wt%) or electrolyte blends with ratio EC to (DMC + EMC) ⁇ 1 LiPF 6 can be used alone or in combination with other conductive salts.
- the latter include, by way of example, LiBF 4 , LiAsF 6 , LiClO 4 , LiB (C 6 H 5 ) 4 , Li CH 3 SO 3 , Li CF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiAlCl 4 , LiSiF 6 , Li [(OCO) 2 ] 2 B, LiDFOB, LiCl, and LiBr.
- LiBF 4 LiAsF 6 , LiClO 4 , LiB (C 6 H 5 ) 4 , Li CH 3 SO 3 , Li CF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiAlCl 4 , LiSiF 6 , Li [(OCO) 2 ] 2 B, LiDFOB, LiCl, and LiBr.
- the concentration of LiPF 6 or conductive salt mixtures compared to the non-aqueous solvents is not limited, but should preferably remain within the following range: 0.1 M (mol / dm 3 ) to 5.0 M, preferably 0.5 M to 3.0 M ,
- Materials a and b are added with a mixture of electrolyte and water to enhance the formation of harmful HF and studied by cyclic voltammetry.
- Reference is an electrolyte (ethylene carbonate: dimethyl carbonate (1: 1) with 1 mol / L LiPF 6 ) without addition of an inorganic material.
- the effect of HF binding is documented by the evaluation of a peak characteristic for HF at 2.9 V in the cyclovoltagram.
- the decrease in HF concentration is manifested under potential load for both materials, a and b, while in the system Electrolyte with water, the amount of HF even increases towards the end of the experiment (see FIG. 1 ).
- the cathode material LiMn 2 O 4 (LMO) was added to the respective above-mentioned CV measurements in the next step. LMO is destroyed by the reaction with HF, Mn is dissolved out of the crystal compound.
- the evaluation of the CV data (plot of the peak heights) also shows here that the inorganic filler materials getter apart from an electrode material HF.
- the supernatant solution was assayed for Mn 2+ by ICP-OES. This shows that in the sample with material b significantly less Mn is leached from the cathode material in comparison to material a and the system without inorganic additive.
- Electrolyte + Al 2 O 3 Electrolyte + AB17 20
- the getter effect of the material b sets in after a certain time (in CV further significant decrease of the RF peak after 5 cycles). This is necessary because during the formation of a LIB cell, small amounts of HF are needed to form the SEI, as well as to passivate the Al current collector of the cathode.
- materials a and b were stored for 7 days in a moistened electrolyte and then the fluoride content was determined by means of ion chromatography. Material b significantly binds HF during service life.
- a separator coated with the additive (glass powder) was incorporated into cathode half cells (Li / LP301 glass-polyethylene separator / LP30 / cathode material; 1) lithium manganese oxide (LMO) 2) lithium nickel cobalt manganese oxide (NCM)) for battery test.
- Swaglok cells were used for the experiment with a lithium reference. It was cycled according to a CC-CV protocol. Initially, 5 forming cycles are carried out at a current for C / 10 (corresponding to a charging or discharging step of 10 h), then the cells are charged and discharged with a current of 1 C (corresponding to the time of 1 h). The voltage range was 3.0 to 4.4 V.
- the electrolyte LP30 [EC: DMC (1: 1) + 1 mol / L LiPF6] was dry (H 2 O ⁇ 20 ppm).
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PCT/EP2013/062049 WO2014016039A1 (de) | 2012-07-26 | 2013-06-11 | Zusatzstoff für elektrochemische engergiespeicher und elektrochemischer engergiespeicher |
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CN (1) | CN104508875B (ko) |
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EP3063807B1 (de) * | 2013-10-31 | 2019-05-08 | Schott AG | Wiederaufladbarer lithium-ionen akkumulator |
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JP6756624B2 (ja) | 2014-06-23 | 2020-09-16 | ショット アクチエンゲゼルシャフトSchott AG | 板状の別個の要素を有する、蓄電システム、板状の別個の要素、その製造方法、並びにその使用 |
WO2016087311A2 (de) | 2014-12-01 | 2016-06-09 | Schott Ag | Elektrisches speichersystem mit einem scheibenförmigen diskreten element, diskretes scheibenförmiges element, verfahren zu dessen herstellung sowie dessen verwendung |
EP3353844B1 (en) | 2015-03-27 | 2022-05-11 | Mason K. Harrup | All-inorganic solvents for electrolytes |
CN106410131B (zh) * | 2015-07-30 | 2020-08-07 | 权镐真 | 锂二次电池用正极活性物质及其制备方法以及锂二次电池 |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
JP7144403B2 (ja) * | 2017-03-31 | 2022-09-29 | 株式会社エンビジョンAescジャパン | 電池用電極及びリチウムイオン二次電池 |
CN109742403A (zh) * | 2019-01-16 | 2019-05-10 | 欣旺达电子股份有限公司 | 捕捉氢氟酸的浆料制备方法及锂离子电池 |
CN114867696B (zh) * | 2019-12-27 | 2024-07-02 | 微宏动力系统(湖州)有限公司 | 包含固体颗粒的电解液及锂离子二次电池 |
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JPH11224676A (ja) * | 1998-02-06 | 1999-08-17 | Yuasa Corp | リチウム電池 |
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US20150207184A1 (en) | 2015-07-23 |
KR20150037764A (ko) | 2015-04-08 |
WO2014016039A1 (de) | 2014-01-30 |
DE102012215824A1 (de) | 2014-11-13 |
US11342593B2 (en) | 2022-05-24 |
KR102005606B1 (ko) | 2019-07-30 |
EP2878023A1 (de) | 2015-06-03 |
CN104508875A (zh) | 2015-04-08 |
JP2015532762A (ja) | 2015-11-12 |
JP6378176B2 (ja) | 2018-08-22 |
CN104508875B (zh) | 2018-01-23 |
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